U.S. patent number 3,622,362 [Application Number 04/766,001] was granted by the patent office on 1971-11-23 for alcohol soluble cellulose propionate ester.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Chester A. Bruner, Charles H. Coney, Thomas J. Thompson.
United States Patent |
3,622,362 |
Coney , et al. |
November 23, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
ALCOHOL SOLUBLE CELLULOSE PROPIONATE ESTER
Abstract
Cellulose propionate compositions having a propionyl content of
from about 37 to about 44 percent by weight, a free hydroxylcontent
from about 3.5 to about 8 percent by weight and an ASTM D-1343
viscosity of from about 0.02 to about 50 seconds, have been found
to be soluble in hydrous ethanol at 70.degree. F. These
compositions are especially useful in ink formulations.
Inventors: |
Coney; Charles H. (Kingsport,
TN), Thompson; Thomas J. (Kingsport, TN), Bruner; Chester
A. (Kingsport, TN) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
25075107 |
Appl.
No.: |
04/766,001 |
Filed: |
October 8, 1968 |
Current U.S.
Class: |
536/68;
106/31.37; 106/31.69 |
Current CPC
Class: |
C08B
3/08 (20130101); C08B 3/24 (20130101); C09D
11/14 (20130101) |
Current International
Class: |
C08B
3/24 (20060101); C08B 3/08 (20060101); C08B
3/00 (20060101); C09D 11/14 (20060101); C08b ();
C09j 003/04 () |
Field of
Search: |
;106/26,169,189,196,193
;260/13-17,227,230,224 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Evans; Joan B.
Claims
We claim:
1. Cellulose propionate characterized by being soluble in hydrous
ethanol at 70.degree. F. having a propionyl content of from about
37 percent to about 44 percent by weight, a free hydroxyl content
from about 4.4 percent to about 8 percent by weight, and an ASTM
D-1343 viscosity of from about 0.02 to about 50 seconds, wherein
the cellulose propionate is substantially free of significant
amounts of acetyl which may be present in said cellulose propionate
as an impurity.
2. The composition of claim 1 wherein the ASTM D-1343 viscosity is
between about 0.02 and about 5.0 seconds.
3. The composition of claim 1 wherein the ASTM D-1343 viscosity is
between about 0.02 and 1.5 seconds.
Description
This invention concerns new alcohol soluble cellulose propionate
ester compositions and their preparation.
The preparation of cellulose propionate, both the triester and
certain hydrolyzed propionates, have been known for some time.
Dreyfuss and Schneider describe the preparation in U.S. Pat. No.
1,824,877. In their work they prepared a cellulose propionate and
described its solubility in a series of solvents. Their material
was soluble in hot ethanol, but insoluble in cold hydrous ethanol,
that is, 70.degree. F. ethanol. A later patent, U.S. Pat. No.
2,076,555, describes a cellulose propionate soluble in a series of
solvents including a mixture of 62 percent acetone, 21 percent
butyl acetate, and 17 percent ethyl alcohol. The primary solvent
for these esters was acetone and the esters were insoluble in
benzene. It is recognized in the art that cellulose propionate
esters are not soluble in cold alcohol, that is, 70.degree. F.
ethanol.
In the printing of essentially nonpermeable, nonporous webs,
plastic films and metal toils, a fast evaporating solvent system is
very desirable in order that the printed ink may be dried in the
short time allowed during the printing process. Low molecular
weight alcohols such as ethyl alcohol are most desirable in
flexographic and gravure printing processes because they not only
evaporate rapidly but also have little or no effect on rubber
rolls. In fact, flexographic printing is limited to only alcohols
or high alcohol content solvent systems.
Several film forming polymers are available which have sufficient
alcohol solubility to serve as the pigment binding portion of flexo
inks. Two typical resins are nitrocellulose and polyamide. The
novel, alcohol soluble, propionic acid ester of cellulose described
herein has several distinct and desirable advantages over these
typical resins and over other resins known to be employed in the
printing ink field.
Objects of the present invention are to provide cellulose
propionate compositions soluble in certain ethanol based solvents
and having certain characteristics such as: solubility in certain
cold hydrous ethyl alcohol; particular suitability for application
in flexographic and other types of printing inks; odorless resins
useful in printing inks, overprints, and coating lacquers; enhanced
adhesion to treated polyethylene, treated polypropylene, and other
plastic substrates; and capability of producing a high degree of
surface gloss when serving as the principal film former in
pigmented compositions.
These and other objects hereinafter appearing have been attained in
accordance with the present invention through the discovery that
certain cellulose propionate compositions are soluble in certain
cold mixtures of ethanol and water and can be prepared from
cellulose propionate by a certain hydrolysis procedure hereinafter
described in detail. The cold ethanol/water weight proportion
ranges from about 3/100 to about 20/100. These novel cellulose
propionates are also soluble in conventional cellulose esters
solvents such as acetone, ethyl acetate, methyl ethyl ketone, and
the ethylene and diethylene glycol ethers and ether acetates, and
blends of these with other solvents or nonsolvents.
The cellulose propionate which can be hydrolyzed according to the
present invention may be prepared by the propionation of cellulose
by conventional procedures to give a propionyl group content of
from about 46 to about 50 percent by weight as measured by ASTM
D-817-62, Sections 20-27. The propionation is essentially complete,
with possibly insignificant amounts of sulfate, or other acyl
groups present such as acetyl, butyryl or benzoyl, which may enter
the esterfication reaction as impurities in the commercial
reactants.
The various sources of cellulosic materials which may be employed
in the present invention include cotton and wood pulp. A discussion
of cellulose is found in High Polymers, Vol. 5, Chapters 1-3 of
Emil Ott, Harold M. Spurlin and Mildred W. Grafflin Interscience
Publishers, 1954, Second Edition, wherein it is specifically
defined as comprising at least 700 anhydroglucose units,
specifically anhydroglucose-pyranose units.
A typical preparation of cellulose propionate involves slurrying
acetylation grade wood pulp in water for activation, and
centrifuging to give a water/cellulose weight proportion of from
about 1/2 to 5/1. Other proportions can, of course, be employed, as
well as the undried mill cellulose. The wet cellulose is then
dewatered by suitable means such as replacement by propionic acid.
This step is preferred since water would impede the subsequent
esterification by reaction with the propionic anhydride.
The dewatered cellulose is then charged to an acylation mixer,
preferably provided with cooling means to prevent uncontrolled
cellulose degradation during esterification. Propionic anhydride,
preferably cold, in excess is added to the acylation mixer along
with propionic acid and dry sulfuric acid catalyst. The propionic
acid serves, among other purposes, as a convenient reaction medium.
The acylation reaction is initiated by addition of the sulfuric
acid catalyst last, or by addition of all reactants at the same
time. The temperature is preferably kept below about 150.degree. F.
Reaction time for essentially complete propionation depends, of
course, on reaction conditions including reactant concentrations.
From about 4 to about 6 hours would be considered an adequate
reaction time.
The hydrolysis may be carried out by known methods including either
acid or basic hydrolysis. A preferred acid hydrolysis involves the
use of sulfuric acid catalyst, and aqueous propionic acid (90
percent acid) to prevent ester precipitation, in an agitated vessel
at temperatures not exceeding about 200.degree. F. The hydrolysis
must be carefully regulated to give a propionyl content of from
about 37 to about 44 percent by weight, and a free-hydroxyl content
of from about 3.5 to about 8.0 percent by weight. A hydrolysis time
of from about 18 to about 24 hours has been found adequate at
temperatures of from about 125.degree. F. to about 200.degree. F.
The hydrolysis time required, however, is dependent upon such
factors as temperature, acid concentration, sulfuric acid catalyst
concentration, and the like. The hydroxyl content is measured by
ASTM D-817-62, Sections 28-33, and the propionyl content as stated
above.
The solution viscosity of these cellulose propionate compositions
can vary between about 0.02 and about 50 seconds as measured by
ASTM D-1343, but preferably between about 0.02 to about 5.0
seconds, and particularly from about 0.02 to about 1.5 seconds, and
is determined by the molecular weight change during
esterification
The invention will be further illustrated by the following
examples.
EXAMPLE 1
One hundred parts of cotton linters was slurried in 3000 parts of
water and then centrifuged to a content of about one part of water
per part of cellulose, by weight. The cellulose mass was then
essentially dewatered by spraying propionic acid into the
centrifuge until the acid wet cellulose contained about one part of
acid and 0.01 to 0.03 part of water per part cellulose.
The dewatered cellulose was charged to a jacketed acylation mixer
to which cold propionic anhydride had previously been added. The
reaction mass, having an initial temperature of about 50.degree. F.
was of the following composition:
Component Parts by Weight Cellulose (dry weight) 1.00 Propionic
Acid 2.00 Propionic Anhydride 3.40 Sulfuric Acid 0.03
After initiating the reaction, the mass acylated rapidly and
smoothly. The temperature was controlled by jacket cooling and not
allowed to rise over 150.degree. F. In 4 to 6 hours, a smooth,
completely reacted tripropionate ester of the desired viscosity was
obtained.
The anhydride was then reacted with 7 parts aqueous propionic acid
(90 percent acid) to obtain a hydrous media for hydrolysis. The
mass was hydrolyzed in an agitated vessel at temperatures not
exceeding 200.degree. F. for 18- 24 hours. The analysis of this
material was 1.10 sec. ASTM D-1343 viscosity, 38.3 percent
propionyl, and 5.34 percent OH.
EXAMPLE 2
Same procedure was used as in example 1 except that the hydrolysis
was stopped such that the analysis of the ester was 0.09 sec. ASTM
D-1343 viscosity, 37.9 percent propionyl, and 6.2 percent OH.
EXAMPLE 3
Same procedure as example 1 giving an ester with analysis of 0.5
sec. ASTM D-1343 viscosity, 41.7 percent propionyl, and 4.4 percent
OH.
EXAMPLE 4
Same procedure as example 1 giving an ester with analysis of 0.5
sec. ASTM D-1343 viscosity, 41.7 percent propionyl, and 4.4percent
OH.
EXAMPLE 5
Same procedure as example 1 giving an ester with analysis of 0.60
sec. ASTM D-1343 viscosity, 42.4 percent propionyl, and 3.54
percent OH. This ester was not soluble in ethyl alcohol.
EXAMPLE 6
A thermoplastic flexographic printing ink was prepared by
dissolving 27.9 parts of a 60/40 two-roll mill chip dispersion of
chrome yellow pigment/cellulose propionate resin, as prepared in
example 4 and having a propionyl content of 29.2 percent, a
hydroxyl content of 5.4 percent, and an ASTM D-1343 viscosity of
0.14; 2.4 parts of sucrose acetate isobutyrate (SAIB); and 9.7
parts of an acrylic copolymer resin consisting of 80 percent ethyl
methacrylate and 20 percent methyl acrylate in 54 parts of 95
percent proprietary, denatured ethyl alcohol, and then adding six
parts of 2-nitropropane. This ink was printed without further
dilution on a flexographic press to yield a printed surface with a
medium gloss. Good adhesion was obtained on a treated
polypropylene, vinylidene chloride coated cellophane, polystyrene,
clay coated paper, and heat-shrinkable vinylidene chloride
films.
EXAMPLE 7
Example 6 was repeated except that 8.3 parts of a phenolic resin
(Durez 12687 a copolymer of about 8/92 hexamethylene
tetramine/resoroinol) was substituted for the 9.7 parts of acrylic
resin. A very glossy print was obtained from this ink (60.degree.
gloss meter reading of 83) and adhesions to treated polyethylene
and treated polypropylene were excellent.
EXAMPLE 8
A thermosetting type flexographic and gravure ink was prepared by
dissolving 30.3 parts of a 60/40 dispersion of chrome yellow
pigment/cellulose propionate resin, said resin having a propionyl
content of 39.2 percent, hydroxyl content of 5.4 percent, and an
ASTM D- 1343 viscosity of 0.14, in a mixture of 2.7 parts of SAIB,
43.6 parts of anhydrous, denatured ethyl alcohol and 4.9 parts of
ethyl acetate. After complete solution was obtained, 0.6 parts of
p-toluene sulfonic acid was added as a catalyst. This ink, having a
viscosity of 190 centipoise, was printed flexographically on
treated polyethylene and polypropylene and cured for 5 seconds at
300.degree. F. The resulting print was glossy, had good adhesion to
both surfaces, and was insoluble in acetone, methyl ethyl ketone,
ethyl acetate, and toluene during a 24-hour period of contact.
EXAMPLE 9
A clear, flexographic overprint was prepared by dissolving 20 parts
of the cellulose propionate having a propionyl content of 39.2
percent, hydroxyl content of 5.4, and an ASTM D-1343 viscosity of
0.14 in 80 parts of 95 percent ethyl alcohol. This overprint was
applied to a paperboard with a flexographic press and a glossy,
protective finish was obtained.
A typical composition range for printing ink utilizing an
alcohol-soluble cellulose propionate resin is: Pigment or Dye
Component Parts by Weight Cold Hydrous Ethanol 1 Soluble Cellulose
Propionate Resin up to 40 Solvent (cold ethanol to 99 containing 5%
water) Pigment or Dye up to 50
Among the modifying resins useful in ink formulations may be
mentioned urea-formaldehyde, melamine-formaldehyde, acrylics,
polyvinyl acetate, polyesters, polyamides, phenolics, natural such
as wood rosins and resins, and epoxides. The higher solvent
contents are, of course, required for the higher resin solids
content.
Cellulose propionates having a propionyl content of 38- 42 percent,
a hydroxyl content of from 4- 8 percent, ASTM D-1343 viscosities
from 0.05 to 2 seconds are particularly useful in ink
formation.
Among the various useful pigments or dyes may be mentioned are
Ti0.sub.2, carbon black, the various metal compound pigments such
as cadmium sulfide, zinc oxide, zinc sulfide, chromium oxide, iron
oxide, selenium sulfide, the organic colorants such
phthalocyanines, pyrozolones, quinacridones, alizarines and
rhodamines.
The treated polyethylene and polypropylene films referred to above
are those rendered more receptive to organic based inks and
coatings by exposure of the polyolefin surface to corona discharge,
oxidizing flame, or halogenated organic liquids such as ethylene
chloride.
This invention has been described in detail with particular
reference to specific embodiments thereof, and it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention as described hereinabove and
as defined in the appended claims.
* * * * *